Process for preparing spiro compounds

ABSTRACT

A spiro compound having the general formula   WHEREIN Z1 is a bonding group which forms a lactone and is selected from the group consisting of -CH2)n, which n is an integer of from 2 to 4;   WHEREIN Z2 is a bonding group -CH2 m, in which m is an integer of from 3 to 6, forming an alicyclic paraffin ring; and wherein R1 and R2 are each an alkyl group having from 1 to 3 carbon atoms. These compounds are useful in photography.

United States Patent [1 1 Mukaiyama et al.

Mar. 4, 1975 i 1 PROCESS FOR PREPARING SPIRO COMPOUNDS [75] Inventors: Teruaki Mukaiyama, Tokyo;

Moriaki Higo; Harumi Katsuyama, both of Saitama, all of Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Mar. 16, 1972 [21] Appl. No.: 235,320

[30] Foreign Application Priority Data Mar. l7, 1971 Japan 46-l4842 [52] US. Cl 260/347.8, 260/333, 260/345.9 [51] Int. Cl C07d 5/04 [58] Field of Search 260/3459, 333, 347.8

[56} References Cited OTHER PUBLICATIONS Mukayaima et. al., Tetrahedron Letters Sept. 1971, N0. 40, pp 3697-3700 Takei et. al., Bulletin of the Japanese Chemical Society vol. 41, No. 7, July 1968, p. I738 Prinmry Examiner-Henry R. Jiles Assismnt E.\'aminerBernard l. Dentz Attorney, Agent, or Firm-Sugrue, Rothwell, Mion. Zinn & Macpeak [57] ABSTRACT A spiro compound having the general formula 9 9 C &"\ Z! \C/ l o T Z wherein Z is a bonding group which forms a loctone and is selected from the group consisting of {CH@,,, which n is an integer of from 2 to 4;

CH =([J-; and CRI -(6W; CITI 7 CH- wherein Z is a bonding group -CH in which n1 is an integer of from 3 to 6, forming an alicyclic paraffin ring; and wherein R and R are each an alkyl group having from 1 to 3 carbon atoms. These compounds are useful in photography,

10 Claims, N0 Drawings 1 PROCESS FOR PREPARING SPIRO COMPOUNDS BACKGROUND OF THE INVENTION The present invention relates to a process for preparraphy and as intermediate products for producing nonsilver salt photographic sensitive materials.

The spiro compounds of the present invention are new compounds which have not been described previing new spiro compounds. 5 ously in the literature. The reaction of the present invention in which a methylene carbon atom of the sulfo- SUMMARY OF THE INVENTION nium ylide is inserted beween the carbonyl carbon In more detail, the present invention relates to a proom an he oxygen atom of the lactone is a new type cess for preparing new spiro compounds of the general of reaction which is very interesting in synthetic orformula (III) comprising reacting a stable cyclic sulfol ganic hemistry. There is no case excepting using carniu ylide f th general f l (I), h as ketene bene in which a reaction for inserting methylene cardimer, B-propiolactone and 'y-butyrolactone, und r bon atoms into many kinds of bonds is observed often. mild temperature conditions by a new reaction in ac The Structure of the Spiro compounds P p y cordance with the following reaction scheme (l) in the p invention was determined using y yp which a methylene carbon atom of the cyclic sulfonium of instrumental analyses Such as elementary y ylide is inserted between the carbonyl carbon atom and infrared absorption Spectrum mass spectrum and the oxygen atom of the lactone while splitting off a sul- Clear magnetic resonance Spectrum analyses fid Reaction Scheme 1 In the following, the above-mentioned point is de- 0 O i 1 0 l R' R SR O \,C- S \/O Z 2 (I) (II) (III) wherein Z, is a bonding group which forms a lactone, such as +CH (n=2, 3 or 4),

CH 3 or CH -(l1: CH

Z is a bonding group which forms an alicyclic paraffin, such as (-CH )m (m=3, 4, 5 or 6) R and R are. each an alkyl group having from 1 to 3 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION As the cyclic sulfonium ylide, dimethylsulfonium-2- oxo-cyclopentylide, diethylsulfonium-Z-oxocyclohexylide, dimethylsulfonium-Z-oxocyclohexylide, dimethylsulfonium-2-oxo-heptylide and dimethylsulfonium-2-oxo-cyclooctylide and the like, are suitable.

The reaction can be conducted both in the presence 'or absence of a solvent.

. and carbon tetrachloride, are suitable. The preparation of the spiro compounds of the present invention can be carried out at a reaction temperature ranging from about -50C to about 100C. But about room temperature (about to C) is generally preferable.

The products prepared by the process of the present invention can be used as an additive for silver salt photography, an image stabilizer for non-silver salt photogscribed. In an example of a spiro compound in which Z in the formula is This compound was a white crystal having a melting point of 84.586.0C. By elementary analysis, a carbon of 66.66 percent and a hydrogen of 6.70 percent were determined which coincided with the calculated value for C H O that is, a carbon of 66.65 percent and a hydrogen of 6.71 percent. The molecule ion peak of the mass spectrum was 180. Thus, the composition and the molecular formula of the compound were confirmed.

Using the infrared absorption spectrum, strong absorptions at l724cm" due to the stretch vibration of the carbonyl group, l690cm due to the stretch vibration of the 0a,,B-unsaturated ketone and l6l0cm due to the stretch vibration of the carbon to carbon double bond were observed. Using nuclear magnetic resonance spectrum, absorptions at 1.5 to 3.1 ppm belonging to the methylene group corresponding to 8H, 2.29ppm (3H) belonging to the methyl group and 5.27ppm (1H) belonging to the hydrogen atoms bonded to the carbon-carbon double bond were observed. Further, in the ultraviolet absorption spectrum, an absorption maximum at 266mg, (e 9500, methanol) was observed which affirmed the presence of the a,,B-unsaturated ketone.

As the result of the above-described determinations, it'became clear that the structure of this compound was 2,3-dihydro-5-methyl-3-oxo-spiro(furan-2,2'- cyclohexanone).

In the following, the reaction of the preseiitinvention Journal of the Chemical Society 133, 713 (1930)).

Recently, new active sulfur ylides have been synthesized and separated as stable crystals by Corey (see Journal of the American Chemical Society 84, 867 (1962)) Franzen (see Chemische Berichte 96, 1881 (1963)) and Nozaki (see Tetrahedron Letters, 251 (1965)). Since then, numerous studies have been done and application to synthetic organic reactions has been reported widely (see A. W. Johnson Ylid Chemistry (1966), Academic Press, New York).

The present invention has resulted from studies, carried out over several years. Namely, the reaction of the present invention has been found by considering the fact that cyclic sulfonium ylides react in good yields with acetylene compounds under very mild conditions to form ring expanded sulfonium products in which a two carbon atoms increase in the ring occurs.

In the following, the reaction of the present invention will be explained in greater detail by reference to the following examples, which should be considered as i1- lus'trative rather than limiting in any manner.

SYNTHESIS EXAMPLE 1 Synthesis of cyclic sulfonium ylide a. Synthesis of sulfonium salt from a halogenoketone: A sulfonium salt was produced using the method of Pettitt (as described Journal of Organic Chemistry 29, 2702 (1964)) in which a sulfonium salt was obtained by reacting a 2-halogeno alicyclic ketone synthesized conventionally (for example, 2-bromocyclopentanone, 2-bromocyclohexanone, 2-bromocycloheptanone and 2-bromocyclooctanone) with dimethylsulfide in the presence of a silver salt of 2,4,6-trinitrobenzene sulfonic acid or silver borofluoride, or a method of reaction with the sodium salt of methylmercaptan and separating the sulfonium salt using dimethyl sulfate. b. Synthesis of sulfonium ylide from the sulfonium salt: A saturated aqueous solution of potassium carbonate in which a 50 percent aqueous solution of sodium hydroxide was suspended was added to a chloroform solution of the sulfonium salt while cooling with ice. After stirring for 30 minutes, the chloroform layer was separated and dried using potassium carbonate. Then, it was concentrated to produce a sulfonium ylide.

Structure of the resulting sulfonium ylide:

Yield, the melting point and the infrared absorption spectrum of the resulting sulfonium ylide are shown in Table 1.

Table 1 Infrared Absorp- I Substituent Yield Melting Point tion Spectrum (z Only stable in solution, and impossible to separate at room temperature) SYNTHESIS EXAMPLE 2 Synthesis of 2,3-dihydro-5-methyl-3-oxo-spiro (furan-2,2 '-cyclohexanone) To a suspension of dimethylsulfonium-2'oxocyclohexylide (0.79g, 5.0 111 mol) in benzene, a benzene solution (8 ml) of ketene dimer (0.42g, 50 m mol) was added at room temperature. Since the reaction proceeded exothermically the crystals of dimethylsulfonium-2-oxo-cyclohexylide disappeared and a transparent light yellow solution was obtained. After stirring at room temperature for 10 hours, the mixture was heated to 65C for an hour in order to complete the reaction. After removing the benzene by distillation under a reduced pressure, 0.85g of white crystals of 2,- 3-dihydro-5-methy1-3-oxospiro (furan-2,2- cyclohexanone) was obtained, the yield of which was 94 percent.

In this compound, Z was CH;,- C CH and Z was CH The structure was the same as that in Synthesis Example 1.

SYNTHESIS EXAMPLE 3 Synthesis of 2,3-dihydro-5-methyl-3-oxo-spiro (furan-2,2 '-cycloheptanone) Table 2 Melting Point (C) 106 Elementary Analysis (7c) C: 67.76, H: 7.17 Calculated Value as C: 68.02, H: 7.27 n n a Infrared Absorption 1727 (y C 0), Spectrum (cm") 1682 ('y C C C O),

1602 (y C C) 1.2 2.6 (8H multiple lines) 2.32 (3H, S), 2.98 (2H, d), (ppm) 5.31 (1H, S)

Ultraviolet Absorption A 266 (e 9100, methanol) Spectrum (mp) max Nuclear Magnetic Resonance Spectrum In this compound, Z is CH --C CH and Z is (CH SYNTHESIS EXAMPLE 4 Synthesis of 3-oxo-spiro(tetrahydropyran-2,2 '-cyclohexanone) the formula (I) 6 3-Oxo-spiro(tetrahydropyran-2,2'-cyclohexanone) C O was produced as white crystals in a yield of 50 percent 2 R (1) by reacting dimethylsulfonium-2-oxo-cyclohexylide E s with 'y-butylolactone in the same manner as described in Synthesis Example 2 and removing the benzene from 5 the resulting oily substance using a silica gel column With a lactone 0f the formula (Wakogel C 200, made by Wako Junyaku Co.). The result of the analyses are shown in Table 3. C O

1 Table 3 m r z 0 Melting Point (C) 50 Table 3-Continued wherein Z is selected from the group consisting of Elementary Analys1s(%) c: 65.90, H; 7.72 2)r. in which n is n n g r f r m 2 to 4; Calculated Value as C: 65.91, H: 7.74 15 ul H 3 Infrared Absorption 1727 ('y C i O) CH C Spectrum (cm l720 (y C O) r 2 Nuclear Magnetic Multiple lines at 1.2 2.8 Resonance Spectrum CH (ppm) 2 Ultraviolet Absorption 270 (e 30) Spectrum mm) with the CH end being attached to a keto carbon atom of the spiro compound; and While the invention has been described in term of various examples it will be apparent that changes and CH C modifications can be made without departing from the spirit and scope of the invention. CH-

What is claimed is: 1, A Spiro compound h i th f l with the CH end being attached to a keto carbon atom of the spiro compound; wherein Z is a bonding O O group -(-CH in which m is an an integer of from 3 to 6, forming an alicyclic paraffin ring; and wherein R l' C C C 22511550211122 each an alkyl group having from I to 3 car- O 2 3. The process of claim 2, wherein said cyclic sulfonium ylid e is selected from the group consisting of dimwherein Z, is selected from the group consisting of ethyl-sulfonium-2-oxo-cyclopentylide, diethyl- (-CH in which n is an integer of from 2 to 4; sulfonium-2-oxo-cyclohexylide, dimethylsulfonium-2- 'oxo-cyclohexylide, dimethyl-sulfonium-2-ox0- CHZ ccycloheptylide and dimethylsulfonium-2-oxo- 40 cyclooctylide. 2 4. The process of claim 2, wherein said lactone is selected from the group consisting of ketene dimer, with the CH end being attached to a keto carbon ,B-propiolactone and ybutyrolactone, atom of the spiro compound; and 5. The process of claim 2, wherein said process is conducted in a solvent. CH C- 6. The process of claim 5, wherein said solvent is selected from the group consisting of hydrocarbons, ethers, alcohols and halogenated paraffins.

7. The process of claim 2, wherein said process is with the CH- end being a tac 0 3 keto Carbon conducted at a temperature of from about 50C to atom of the spiro compound; wherein Z is a bonding b u 100C group 2 1m in which m is an integer of from 3 to 8. The process of claim 7, wherein said process is 6, forming an alicyclic p r ffin gconducted at a temperature of from about 20 to about 2. A process for preparing a spiro compound of the 30 formula 9. The spiro compound of claim I, wherein said spiro compound is 2,3-dihydro-5-methyl-3-oxo-spiro (furun- O O 2,2'-cyclohexanone).

10. The process of claim 2, wherein said spiro com- Zf (In) pound of the general formula (III) is 3,3-dihydro-5- 1 methyl-3-oxo-spiro (furan-2,2'-cyclohexanonel,

\ O 2 wherein said cyclic sulfonium ylide of the general formula (I) is dimethyl-sulfonium-2--oxo-cyclohexylide, wherein the lactone of the general formula (ll) is kewhich comprises reacting a cyclic sulfonium yllde of tens dim 

1. A SPIRO COMPOUND HAVING THE FORMULA
 2. A process for preparing a spiro compound of the formula (III)
 3. The process of claim 2, wherein said cyclic sulfonium ylide is selected from the group consisting of dimethyl-sulfonium-2-oxo-cyclopentylide, diethyl-sulfonium-2-oxo-cyclohexylide, dimethylsulfonium-2-oxo-cyclohexylide, dimethyl-sulfonium-2-oxo-cycloheptylide and dimethylsulfonium-2-oxo-cyclooctylide.
 4. The process of claim 2, wherein said lactone is selected from the group consisting of ketene dimer, Beta -propiolactone and gamma -butyrolactone.
 5. The process of claim 2, wherein said process is conducted in a solvent.
 6. The process of claim 5, wherein said solvent is selected from the group consisting of hydrocarbons, ethers, alcohols and halogenated paraffins.
 7. The process of claim 2, wherein said process is conducted at a temperature of from about -50*C to about 100*C.
 8. The process of claim 7, wherein said process is conducted at a temperature of from about 20* to about 30*C.
 9. The spiro compound of claim 1, wherein said spiro compound is 2,3-dihydro-5-methyl-3-oxo-spiro (furan-2,2''-cyclohexanone).
 10. The process of claim 2, wherein said spiro compound of the general formula (III) is 3,3-dihydro-5-methyl-3-oxo-spiro (furan-2,2''-cyclohexanone), wherein said cyclic sulfonium ylide of the general formula (I) is dimethyl-sulfonium-2-oxo-cyclohexylide, wherein the lactone of the general formula (II) is ketene dimer. 